.

lll)

f,-

=-

I t-

~2- ~

E-//c.r

~ C

+-e

- E-/Ar

I +- e E-/A.T

1-

(elJ...r
- e.

I
____
,.J.,.

-, e.

E//4..-i

- E

e- E-/k(7)

A.r

te --/~T

C eel

k:r 1..

-1- E-

k.. r

A.rL

-E-IA.T)

e..

~ e- E-I It. r)

I +- e r=-!Ie..:r

r e.,-

e-/It..T

C. e. Elk/fe-e-Ik')
l

+-

e. e-11tA

e E-/~I
e E-{~

r e.. -G-//t../

--)1-~ ~ - E-L
-

.s

'Z.

tV It.. ~

.s =-

Nk.~1

+-

-e.. e:1Jc-r 1-

e- Eh:r)

IV

<c:.n~cr
(tA.)

VII

_
~o

~e..p~'0Yt ~
-= e- J1 C-ft -~)

e...-Jl'i..

=-

-[-0

e..

c.. b)

Cc..)

?- d

:::::

t-

- ~ll<.r
e.

(.

N /{.T

Ec.

2-

--

@4,.'t--

~(f:

G"""

-n
::::.

R.

~z, - ~c.

I-

~...o-':
Of

,-1- i)~

Dr

+-e--[o/r

'tz.

N A /<. T'L

Ec.

O(
He(CVt.

_1-0
e.

e +-

if-e.

-/

/,)

I -t-e.--Jolr
1<- 10

/0/.,-

I re.-1o!r
=.

I 0 (k);<

<[. J

I '1 (r lc- - (

~,-V

c:::

'J'7/E

tet)

T1-.

1-'

101,
e
c.. e \o/r +.!J
J k.-I~-'

/Z. e..
L.

( (-r.e.)

"1-

_1..7

It<-.&. I-G.";VI
h-t

:::.

2.-6/

b4

I'

a.J.of4.v't..~

u--;f-

6.,

2 b X 10-.]

=lO"

XI-G.{;

/I. '"

(~1f X

!~

I X

(7-12..

10

-7

Y T..r
;>(lo-~7

:1

Xlo-I/z;)'J

1- If J ~ 'i'

u:: Ce-rV

T Ck.)

_
~

X lj-//6

1/.
X{o

_ 2./ -)

:r

'?J-

(s)

t:.~

1
( eJ.4JA![..r

+ e.

'./

- J1f1 (J/ ,

~.> =

J4. a

e..-..J-tt, n I /c.. r

e -..1..ta

2.;x'l.Z.7'1Xlo

J1.I. 11/A.r)

-2.'1

(j /

:;,

It. T

-I

----------_.
/-381 X 1 -1.1. T
0

I-..!.. ) e.. -

f1

J.... L 7)'

+-

~A

..!4l (J

lit.T

e....

.xl-Ot
k. -/

J.. T

kr)

4
.J4.

11/ j...T

0! k)

/j/

(-N e.

..J.l.lJ Il / j(.'

e..J.L,

.il.IJ

0-7/

6. Write down the molecular partition function with and without degeneracy factor. How
is molecular partition function related to canonical partition function for distinguishable
and indistinguishable particles?

Solution:

q =

e - fJsi

levels, ;
Qtotal

fJs
g;e- ;

levels, i

q t~tal
N

Qtotal

qtotal

N!

7. Calculate the ratio of translational partition functions ofH2 and

K confined separately to a volume of2.0 cm3. Ans: 2.83

.
solutlon:
D2
qtrans

H2
qtrans

qtrans

= -3 = 2JrmkT

D2

molecules at 300

)3/2 V

-3

3/2

= ( :::

= 2.828

8. Estimate the rotational partition function for HCI at 25C for J values up to 10. B
for HCI is 10.59 cm -I.

solution:

qrot

= I (2J + l)e-fJhcBJ(J+l)
J

kT
he
qJ=o
rot

23

1.380 xl 0- JK- x 298K

= 206.gem-1
34
8
1
I
6.626x 10- Js x 3 X 10 ms- x 100em mto 10

= 1+ 2.708 + 3.677 + 3.787 + .....+ 0.1896 + 0.0753

D 19.9

9. Calculate the fraction ofN2(g) molecules in the v = 0 and v = 1 vibrational states at

300K, given that hv
kB

= 3374K

Ans: Fraction (v=O) - 1 and Fraction (v=l)-

qvib

= L.J e

-13

II

n=O

= L.J e

))
-/lhc-;' ( v+"2

=e

-/lhC-;'/2 ~

12 L.J e

n=O

-/lhc-;'v

-/lhC~
2

= -l----/lh-C--;,

n=O

Fraction of molcules in vth state,fv

-:-

1O.What is the electronic partition function for a system with two energy levels which
are triply degenerate with energies E) = 0 and E2 = 8. What is its value at T = 0 K.

solution:
qele == ""L...J g}.e -j3s} == 3 + 3e-j3s
}

qele(T

==

OK)

==

3+0 - 3